Preparation method of perfluorobutyl sulfonate and derivative thereof

Abstract

The invention discloses a preparation method of perfluorobutyl sulfonate and derivatives thereof, and perfluorobutyl sulfonyl fluoride and fluorine-containing alcohol or fluorine-containing phenol are heated to react under normal pressure in the presence of a solvent and alkali to prepare the perfluorobutyl sulfonate and the derivatives thereof. The industrial product perfluorobutylsulfonyl fluoride is selected as a raw material, the method has the advantages of simplicity in operation, cheap and easily available reagents, environmental friendliness and the like, the highest yield can reach 95%, and industrial production is facilitated.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemical synthesis, and specifically relates to a preparation method of perfluorobutyl sulfonate and its derivatives. Background Art

[0002] Perfluorobutyl sulfonate and its derivatives are a new class of ester compounds, and there are few related research reports. According to our research, compared with other esters, it has the following advantages:

[0003] 1. Can be used as a high-quality surfactant precursor;

[0004] 2. It contains double hydrophobic groups, fluorine-containing groups and ester groups, and has potential application value.

[0005] Due to the unique advantages of perfluorobutane sulfonate and its derivatives, it is urgent to develop a method for synthesizing perfluorobutane sulfonate and its derivatives. Summary of the invention

[0006] The object of the present invention is to provide a method for preparing perfluorobutane sulfonate and its derivatives in view of the above-mentioned problems.

[0007] The present invention provides a method for preparing perfluorobutane sulfonate and its derivatives, comprising the following steps:

[0008] Under normal pressure, perfluorobutylsulfonyl fluoride and fluorine-containing alcohol or fluorine-containing phenol are heated to react in the presence of a solvent and a base to obtain the perfluorobutylsulfonate and its derivatives, and the reaction equation is shown in Formula 1:

[0009]

[0010] In some embodiments: the fluorine-containing alcohol or phenol is selected from one of the following structural formulas:

[0011]

[0012] In some embodiments: the molar ratio of the perfluorobutyl sulfonyl fluoride to the fluorinated alcohol or fluorinated phenol is not higher than 1:1, preferably, the molar ratio of the perfluorobutyl sulfonyl fluoride to the fluorinated alcohol or fluorinated phenol is 1:(1.1-1.5), the molar ratio of the base to the fluorinated alcohol or fluorinated phenol is not higher than 1:0.1, preferably, the molar ratio of the base to the fluorinated alcohol or fluorinated phenol is 1:(0.1-2), the usage ratio of the perfluorobutyl sulfonyl fluoride to the solvent is 1 mmol:(1-4) mL, preferably, the usage ratio of the perfluorobutyl sulfonyl fluoride to the solvent is 1 mmol:(1-2) mL.

[0013] In some embodiments: the solvent is one or more of ethyl acetate, acetonitrile, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

[0014] In some embodiments, the base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tert-butyl potassium, tert-butyl sodium, triethylamine or cesium carbonate.

[0015] In some embodiments: the atmosphere of the heating reaction is a protective atmosphere or an air atmosphere. Preferably, the atmosphere of the heating reaction is a protective atmosphere.

[0016] In some embodiments: the reaction temperature is 40-150° C.; the reaction time is 8 h to 48 h.

[0017] In some embodiments: the reaction conditions of the reaction are anhydrous; and the selected reagents further include a water removal step.

[0018] In some embodiments: after the reaction is completed, the solvent must be removed by distillation under reduced pressure, and then the product can be obtained by extraction with methyl tert-butyl ether, concentration, and column chromatography.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] The present invention uses industrial raw materials perfluorobutyl sulfonyl fluoride and fluorine-containing alcohol or fluorine-containing phenol as raw materials, and heats the reaction under the condition of a solvent and a base to efficiently prepare perfluorobutyl sulfonate and its derivatives in a one-pot and one-step method. It has the advantages of no need for a catalyst, cheap and easy to obtain raw materials, a wide range of substrates, green and environmental protection, etc., and is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 FIG. 5 is a liquid chromatogram of a perfluorobutane sulfonate derivative in one embodiment of the present invention. DETAILED DESCRIPTION

[0022] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0023] Embodiment 1:

[0024] A method for preparing perfluorobutane sulfonate and its derivatives comprises the following steps:

[0025] Under normal pressure, perfluorobutylsulfonyl fluoride and 4-fluorophenol are heated to react in the presence of solvent ethyl acetate and base sodium hydroxide. The molar ratio of perfluorobutylsulfonyl fluoride and 4-fluorophenol is 1:1.2, the molar ratio of the base to 4-fluorophenol is 1:2, the concentration of 4-fluorophenol in the solvent is 1 mol / L, the atmosphere of the heating reaction is a protective atmosphere, the heating reaction temperature is 100°C; the heating reaction time is 8 hours, and after the reaction is completed, the solvent must be removed by reduced pressure distillation, and then extracted with methyl tert-butyl ether, concentrated, and column chromatography to obtain a perfluorobutyl sulfonate derivative. After the fluorobutyl sulfonate is purified, methyl tert-butyl ether is used as a solvent, and its liquid chromatogram is as follows Figure 1 As shown, the purity can reach 96%.

[0026] The present invention uses industrial raw materials perfluorobutyl sulfonyl fluoride and fluorine-containing alcohol or fluorine-containing phenol as raw materials, and heats the reaction under the condition of a solvent and a base to efficiently prepare perfluorobutyl sulfonate and its derivatives in a one-pot and one-step method. It has the advantages of no need for a catalyst, cheap and easy to obtain raw materials, a wide range of substrates, green and environmental protection, etc., and is conducive to industrial production.

[0027] Finally, it should be noted that: technicians in this industry should understand that the present invention is not limited to the above-mentioned implementation cases. The above-mentioned embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which shall fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing perfluorobutane sulfonate and its derivatives, characterized in that: The following steps are involved: Under normal pressure, perfluorobutylsulfonyl fluoride and fluorine-containing alcohol or fluorine-containing phenol are heated to react in the presence of a solvent and a base to obtain the perfluorobutylsulfonate and its derivatives, and the reaction equation is shown in Formula 1:

2. The preparation method according to claim 1, characterized in that: The fluorine-containing alcohol or phenol is selected from one of the following structural formulas:

3. The preparation method according to claim 2, characterized in that: The molar ratio of the perfluorobutyl sulfonyl fluoride to the fluorinated alcohol or fluorinated phenol is not higher than 1:

1. Preferably, the molar ratio of the perfluorobutyl sulfonyl fluoride to the fluorinated alcohol or fluorinated phenol is 1:(1.1-1.5). The molar ratio of the base to the fluorinated alcohol or fluorinated phenol is not higher than 1:0.

1. Preferably, the molar ratio of the base to the fluorinated alcohol or fluorinated phenol is 1:(0.1-2). The usage ratio of the perfluorobutyl sulfonyl fluoride to the solvent is 1 mmol:(1-4) mL. Preferably, the usage ratio of the perfluorobutyl sulfonyl fluoride to the solvent is 1 mmol:(1-2) mL.

4. The preparation method according to claim 1, characterized in that: The solvent is one or more of ethyl acetate, acetonitrile, dichloromethane, chloroform, chlorobenzene, toluene, benzene, tetrahydrofuran or 1,2-dichloroethane.

5. The preparation method according to claim 1, characterized in that: The base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tert-butyl potassium, tert-butyl sodium, triethylamine or cesium carbonate.

6. The preparation method according to claim 1, characterized in that: The atmosphere of the heating reaction is a protective atmosphere or an air atmosphere. Preferably, the atmosphere of the heating reaction is a protective atmosphere.

7. The preparation method according to claim 1, characterized in that: The reaction temperature is 40-150° C. and the reaction time is 8-48 hours.

8. The preparation method according to any one of claims 1 to 7, characterized in that: The reaction conditions for this reaction are anhydrous; the reagents selected also include a water removal step.

9. The preparation method according to any one of claims 1 to 7, characterized in that: After the reaction is completed, the solvent must be removed by distillation under reduced pressure, and then the product can be obtained by extraction with methyl tert-butyl ether, concentration and column chromatography.

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